Pirólise termoquímica de pós da fibra de coco seco em um reator de cilindro rotativo para produção de bio-óleo

This master thesis aims at developing a new methodology for thermochemical degradation of dry coconut fiber (dp = 0.25mm) using laboratory rotating cylinder reactor with the goal of producing bio-oil. The biomass was characterized by infrared spectroscopy with Fourier transform FTIR, thermogravimetric analysis TG, with evaluation of activation energy the in non-isothermal regime with heating rates of 5 and 10 °C/min, differential themogravimetric analysis DTG, sweeping electron microscopy SEM, higher heating value - HHV, immediate analysis such as evaluated all the amounts of its main constituents, i.e., lignin, cellulose and hemicelluloses. In the process, it was evaluated: reaction temperature (450, 500 and 550oC), carrier gas flow rate (50 and 100 cm³/min) and spin speed (20 and 25 Hz) to condensate the bio-oil. The feed rate of biomass (540 g/h), the rotation of the rotating cylinder (33.7 rpm) and reaction time (30 33 min) were constant. The phases obtained from the process of pyrolysis of dry coconut fiber were bio-oil, char and the gas phase non-condensed. A macroscopic mass balance was applied based on the weight of each phase to evaluate their yield. The highest yield of 20% was obtained from the following conditions: temperature of 500oC, inert gas flow of 100 cm³/min and spin speed of 20 Hz. In that condition, the yield in char was 24.3%, non-condensable gas phase was 37.6% and losses of approximately 22.6%. The following physicochemical properties: density, viscosity, pH, higher heating value, char content, FTIR and CHN analysis were evaluated. The sample obtained in the best operational condition was subjected to a qualitative chromatographic analysis aiming to know the constituents of the produced bio-oil, which were: phenol followed by sirigol, acetovanilona and vinyl guaiacol. The solid phase (char) was characterized through an immediate analysis (evaluation of moisture, volatiles, ashes and fixed carbon), higher heating value and FTIR. The non-condensing gas phase presented as main constituents CO2, CO and H2. The results were compared to the ones mentioned by the literature.

Estudo da influência da temperatura na degradação termoquímica da biomassa de avelós

The bio-oil obtained from the pyrolysis of biomass has appeared as inter-esting alternative to replace fossil fuels. The aim of this work is to evaluate the influence of temperature on the yield of products originating from the pyrolysis process of the powder obtained from the dried twigs of avelós (Euphorbia tirucalli), using a rotating cylinder reactor in laboratory scale. The biomass was treated and characterized by: CHNS, moisture, volatiles, fixed carbon and ashes, as well as evaluation of lignin, cellulose and hemicellulose, besides other instrumental techniques such as: FTIR, TG/DTG, DRX, FRX and MEV. The activation energy was evaluated in non-isothemichal mode with heating rates of 5 and 10 oC/min. The obtained results showed biomass as feedstock with potential for biofuel production, because presents a high organic matter content (78,3%) and fixed-carbon (7,11%). The activation energy required for the degradation of biomass ranged between 232,92 392,84 kJ/mol, in the temperature range studied and heating rate of 5 and 10°C/min. In the pyrolysis process, the influence of the reaction temperature was studied (350-520 ° C), keeping constant the other variables, such as, the flow rate of carrier gas, the centrifugal speed for the bio-oil condensationa, the biomass flow and the rotation of the reactor. The maximum yield of bio-oil was obtained in the temperature of 450°C. In this temperature, the results achieved where: content of bio-oil 8,12%; char 32,7%; non-condensed gas 35,4%; losts 23,8%; gross calorific value 3,43MJ/kg; pH 4,93 and viscosity 1,5cP. The chromatographic analysis of the bio-oil produced under these conditions shows mainly the presence of phenol (17,71%), methylciclopentenone (10,56%) and dimethylciclopentenone (7,76%)

Estudo da influência da temperatura na degradação termoquímica da biomassa de avelós (euphorbia tirucalli Linn)

The bio-oil obtained from the pyrolysis of biomass has appeared as inter-esting alternative to replace fossil fuels. The aim of this work is to evaluate the influence of temperature on the yield of products originating from the pyrolysis process of the powder obtained from the dried twigs of avelós (Euphorbia tirucalli), using a rotating cylinder reactor in laboratory scale. The biomass was treated and characterized by: CHNS, moisture, volatiles, fixed carbon and ashes, as well as evaluation of lignin, cellulose and hemicellulose, besides other instrumental techniques such as: FTIR, TG/DTG, DRX, FRX and MEV. The activation energy was evaluated in non-isothemichal mode with heating rates of 5 and 10 oC/min. The obtained results showed biomass as feedstock with potential for biofuel production, because presents a high organic matter content (78,3%) and fixed-carbon (7,11%). The activation energy required for the degradation of biomass ranged between 232,92 392,84 kJ/mol, in the temperature range studied and heating rate of 5 and 10°C/min. In the pyrolysis process, the influence of the reaction temperature was studied (350-520 ° C), keeping constant the other variables, such as, the flow rate of carrier gas, the centrifugal speed for the bio-oil condensationa, the biomass flow and the rotation of the reactor. The maximum yield of bio-oil was obtained in the temperature of 450°C. In this temperature, the results achieved where: content of bio-oil 8,12%; char 32,7%; non-condensed gas 35,4%; losts 23,8%; gross calorific value 3,43MJ/kg; pH 4,93 and viscosity 1,5cP. The chromatographic analysis of the bio-oil produced under these conditions shows mainly the presence of phenol (17,71%), methylciclopentenone (10,56%) and dimethylciclopentenone (7,76%)

Bio-óleo e biogás da degradação termoquímica de lodo de esgoto doméstico em cilindro rotativo

The objective of this study was to produce biofuels (bio-oil and gas) from the thermal treatment of sewage sludge in rotating cylinder, aiming industrial applications. The biomass was characterized by immediate and instrumental analysis (elemental analysis, scanning electron microscopy - SEM, X-ray diffraction, infrared spectroscopy and ICP-OES). A kinetic study on non-stationary regime was done to calculate the activation energy by Thermal Gravimetric Analysis evaluating thermochemical and thermocatalytic process of sludge, the latter being in the presence of USY zeolite. As expected, the activation energy evaluated by the mathematical model "Model-free kinetics" applying techniques isoconversionais was lowest for the catalytic tests (57.9 to 108.9 kJ/mol in the range of biomass conversion of 40 to 80%). The pyrolytic plant at a laboratory scale reactor consists of a rotating cylinder whose length is 100 cm with capable of processing up to 1 kg biomass/h. In the process of pyrolysis thermochemical were studied following parameters: temperature of reaction (500 to 600 ° C), flow rate of carrier gas (50 to 200 mL/min), frequency of rotation of centrifugation for condensation of bio-oil (20 to 30 Hz) and flow of biomass (4 and 22 g/min). Products obtained during the process (pyrolytic liquid, coal and gas) were characterized by classical and instrumental analytical techniques. The maximum yield of liquid pyrolytic was approximately 10.5% obtained in the conditions of temperature of 500 °C, centrifugation speed of 20 Hz, an inert gas flow of 200 mL/min and feeding of biomass 22 g/min. The highest yield obtained for the gas phase was 23.3% for the temperature of 600 °C, flow rate of 200 mL/min inert, frequency of rotation of the column of vapor condensation 30 Hz and flow of biomass of 22 g/min. The non-oxygenated aliphatic hydrocarbons were found in greater proportion in the bio-oil (55%) followed by aliphatic oxygenated (27%). The bio-oil had the following characteristics: pH 6.81, density between 1.05 and 1.09 g/mL, viscosity between 2.5 and 3.1 cSt and highest heating value between 16.91 and 17.85 MJ/ kg. The main components in the gas phase were: H2, CO, CO2 and CH4. Hydrogen was the main constituent of the gas mixture, with a yield of about 46.2% for a temperature of 600 ° C. Among the hydrocarbons formed, methane was found in higher yield (16.6%) for the temperature 520 oC. The solid phase obtained showed a high ash content (70%) due to the abundant presence of metals in coal, in particular iron, which was also present in bio-oil with a rate of 0.068% in the test performed at a temperature of 500 oC.

Construção e avaliação de uma unidade de ensino potencialmente significativa para o conteúdo de termoquímica

Nos dias atuais, oferecer uma educação para o exercício da cidadania é função primordial das políticas públicas educacionais, conforme estabelece a constituição brasileira e a legislação de ensino. Essa função vem sendo defendida por muitos professores no Ensino Médio, atribuindo-se a disciplina de Química o papel de proporcionar um ensino crítico, participativo, reflexivo e humano. Segundo os documentos oficiais brasileiros para o Ensino de Química, o estudo do conceito de energia deve favorecer o desenvolvimento de competências para que o aluno compreenda a produção e o seu uso em diferentes fenômenos e possam interpretá-los de acordo com modelos explicativos, além de saber avaliar e julgar os benefícios e riscos da produção e do uso de diferentes formas de energia nos sistemas naturais construídos pelo homem, articulando com outras áreas de conhecimento na procura de promover a interdisciplinaridade. As unidades de ensino potencialmente significativas (UEPS), tomam como base um conjunto de teorias de aprendizagem que tem o intuito de promover um ensino com base na aprendizagem significativa e podem ajudar os estudantes nas diferentes relações que um conceito pode ter. Neste sentido, o estudo do conceito da energia a partir do trabalho com UEPS, pode ser uma importante proposta que favorece um ensino de Química na perspectiva construtivista. Assim, o objetivo deste trabalho é construir e avaliar uma proposta didática para o conteúdo de termoquímica na perspectiva das unidades de ensino potencialmente significativas de Moreira com alunos do Ensino Médio de uma escola pública do Município de Campina Grande-PB. Inicialmente a UEPS foi avaliada por 22 professores em formação inicial de duas instituições públicas de ensino superior. Em seguida, ela foi aplicada para 15 alunos do 2° ano da Escola Estadual de Ensino Médio Prof. Raul Córdula, localizada na cidade de Campina Grande-PB. A coleta dos dados para os professores em formação inicial teve como base um instrumento de validação de elaboração de unidades didáticas baseada na Engenharia Didática proposta por Artigue (1996 apud Guimarães e Giordan, 2011). Já para os alunos do ensino médio, os dados foram coletados no decorrer da UEPS e a avaliação final sobre a proposta didática ocorreu através de um questionário tomando como base a escala de Likert e o uso de mapas conceituais. Para a descrição dos dados, foram utilizados os pressupostos da análise de conteúdo de Bardin. Como produto educacional foi elaborado a Unidade de Ensino Potencialmente Significativa e um DVD contendo orientações de como trabalhar com a proposta. Os resultados deste trabalho apontam uma avaliação positiva quanto à proposta de ensino elaborada para a Educação Básica, onde se observa através do instrumento de validação aplicado, que a maioria das respostas atribuídas pelos professores, ficou entre os itens suficiente e mais que suficiente. Em relação aos momentos de aprendizagem dos alunos do Ensino Médio durante a aplicação da UEPS, foi possível observar que a proposta gerou motivação no processo de ensino e aprendizagem dos conceitos da termoquímica, como também se percebe que os mapas conceituais apresentados pelos alunos apresentaram mais proposições conceituais em uma segunda tentativa de elaboração, logo a proposta de ensino foi aprovada por mais de 90 % dos estudantes do nível médio. Portanto fica evidente que a proposta didática contribuiu no processo de ensino aprendizagem, despertando interesse e motivação nos estudantes pelo conteúdo de Termoquímica.

Pirólise termoquímica de pós da fibra de coco seco em um reator de cilindro rotativo para produção de bio-óleo

This master thesis aims at developing a new methodology for thermochemical degradation of dry coconut fiber (dp = 0.25mm) using laboratory rotating cylinder reactor with the goal of producing bio-oil. The biomass was characterized by infrared spectroscopy with Fourier transform FTIR, thermogravimetric analysis TG, with evaluation of activation energy the in non-isothermal regime with heating rates of 5 and 10 °C/min, differential themogravimetric analysis DTG, sweeping electron microscopy SEM, higher heating value - HHV, immediate analysis such as evaluated all the amounts of its main constituents, i.e., lignin, cellulose and hemicelluloses. In the process, it was evaluated: reaction temperature (450, 500 and 550oC), carrier gas flow rate (50 and 100 cm³/min) and spin speed (20 and 25 Hz) to condensate the bio-oil. The feed rate of biomass (540 g/h), the rotation of the rotating cylinder (33.7 rpm) and reaction time (30 33 min) were constant. The phases obtained from the process of pyrolysis of dry coconut fiber were bio-oil, char and the gas phase non-condensed. A macroscopic mass balance was applied based on the weight of each phase to evaluate their yield. The highest yield of 20% was obtained from the following conditions: temperature of 500oC, inert gas flow of 100 cm³/min and spin speed of 20 Hz. In that condition, the yield in char was 24.3%, non-condensable gas phase was 37.6% and losses of approximately 22.6%. The following physicochemical properties: density, viscosity, pH, higher heating value, char content, FTIR and CHN analysis were evaluated. The sample obtained in the best operational condition was subjected to a qualitative chromatographic analysis aiming to know the constituents of the produced bio-oil, which were: phenol followed by sirigol, acetovanilona and vinyl guaiacol. The solid phase (char) was characterized through an immediate analysis (evaluation of moisture, volatiles, ashes and fixed carbon), higher heating value and FTIR. The non-condensing gas phase presented as main constituents CO2, CO and H2. The results were compared to the ones mentioned by the literature.

Desenvolvimento de uma unidade pirolítica com reator de cilindro rotativo: obtenção de bio-óleo

The demand for alternative sources of energy drives the technological development so that many fuels and energy conversion processes before judged as inadequate or even non-viable, are now competing fuels and so-called traditional processes. Thus, biomass plays an important role and is considered one of the sources of renewable energy most important of our planet. Biomass accounts for 29.2% of all renewable energy sources. The share of biomass energy from Brazil in the OIE is 13.6%, well above the world average of participation. Various types of pyrolysis processes have been studied in recent years, highlighting the process of fast pyrolysis of biomass to obtain bio-oil. The continuous fast pyrolysis, the most investigated and improved are the fluidized bed and ablative, but is being studied and developed other types in order to obtain Bio-oil a better quality, higher productivity, lower energy consumption, increased stability and process reliability and lower production cost. The stability of the product bio-oil is fundamental to designing consumer devices such as burners, engines and turbines. This study was motivated to produce Bio-oil, through the conversion of plant biomass or the use of its industrial and agricultural waste, presenting an alternative proposal for thermochemical pyrolysis process, taking advantage of particle dynamics in the rotating bed that favors the right gas-solid contact and heat transfer and mass. The pyrolyser designed to operate in a continuous process, a feeder containing two stages, a divisive system of biomass integrated with a tab of coal fines and a system of condensing steam pyrolytic. The prototype has been tested with sawdust, using a complete experimental design on two levels to investigate the sensitivity of factors: the process temperature, gas flow drag and spin speed compared to the mass yield of bio-oil. The best result was obtained in the condition of 570 oC, 25 Hz and 200 cm3/min, temperature being the parameter of greatest significance. The mass balance of the elementary stages presented in the order of 20% and 37% liquid pyrolytic carbon. We determined the properties of liquid and solid products of pyrolysis as density, viscosity, pH, PCI, and the composition characterized by chemical analysis, revealing the composition and properties of a Bio-oil.

Pirólise rápida catalítica do capim elefante utilizando materiais mesoporosos e óxidos metálicos para deoxigenação em bio-óleo

The fast pyrolysis of lignocellulosic biomass is a thermochemical conversion process for production energy which have been very atratactive due to energetic use of its products: gas (CO, CO2, H2, CH4, etc.), liquid (bio-oil) and charcoal. The bio-oil is the main product of fast pyrolysis, and its final composition and characteristics is intrinsically related to quality of biomass (ash disposal, moisture, content of cellulose, hemicellulose and lignin) and efficiency removal of oxygen compounds that cause undesirable features such as increased viscosity, instability, corrosiveness and low calorific value. The oxygenates are originated in the conventional process of biomass pyrolysis, where the use of solid catalysts allows minimization of these products by improving the bio-oil quality. The present study aims to evaluate the products of catalytic pyrolysis of elephant grass (Pennisetum purpureum Schum) using solid catalysts as tungsten oxides, supported or not in mesoporous materials like MCM-41, derived silica from rice husk ash, aimed to reduce oxygenates produced in pyrolysis. The biomasss treatment by washing with heated water (CEL) or washing with acid solution (CELix) and application of tungsten catalysts on vapors from the pyrolysis process was designed to improve the pyrolysis products quality. Conventional and catalytic pyrolysis of biomass was performed in a micro-pyrolyzer, Py-5200, coupled to GC/MS. The synthesized catalysts were characterized by X ray diffraction, infrared spectroscopy, X ray fluorescence, temperature programmed reduction and thermogravimetric analysis. Kinetic studies applying the Flynn and Wall model were performed in order to evaluate the apparent activation energy of holoceluloce thermal decomposition on samples elephant grass (CE, CEL and CELix). The results show the effectiveness of the treatment process, reducing the ash content, and were also observed decrease in the apparent activation energy of these samples. The catalytic pyrolysis process converted most of the oxygenate componds in aromatics such as benzene, toluene, ethylbenzene, etc

A compreensão de reação química como um sistema complexo a partir da discussão dos erros e dificuldades de aprendizagem de estudantes do ensino médio

The study of chemical reactions is among the most important contents to the understanding of Chemistry discipline in basic education. However, there are still few studies about chemical reactions as a complex system because, generally, this content is presented in textbooks, taught and even researched in a fragmented form. The thesis here presented aims to investigate, identify and characterize the mistakes and learning difficulties of the students about chemical reactions as a complex system, using for that purpose the analysis of the answers of 126 exams of candidates for the bachelor’s degree in Chemistry Teaching on the entrance exam for the Federal University of Rio Grande do Norte (UFRN). The mistakes and learning difficulties about the parameters ΔG°, Kp, Ea and of the calculation of the amount of substance in a chemical reaction have been identified, as well as the levels of development of the ability to interpret the chemical reaction as a system. The main theoretical source of this study is structured based on the mistakes and learning difficulties (NÚÑEZ, RAMALHO, 2012), of the chemical reactions as complex systems (NÚÑEZ, 1994; RESHETOVA, 1988; SANDERSON, 1968). As methodology, it was prioritized the analysis of the answers to the exams and the interview with the teachers. The results showed typical mistakes in the study of this subject, especially low levels and skill development. No student was able to integrate the different aspects in the systemic understanding of the chemical reaction. From the interviews with Chemistry teachers from High School, it was determined the reasons the teachers assign to those mistakes and learning difficulties. The interviews revealed that the teachers do not work in the perspective of integration of the contents which leads the students to present difficulties and make mistakes related to the content previously mentioned. The study presents a proposal for the organization of the contents of Chemistry discipline for High School as a possibility of a dialectic systemic integration of contents, understanding that this systematic vision, leads to important contributions to the development of the theoretical thinking of the students. We can mention as one of the conclusions of this study, the fact that the non-systemic organization of contents do not favor this kind of thinking in students.

Desenvolvimento de uma unidade pirolítica com reator de cilindro rotativo: obtenção de bio-óleo

The demand for alternative sources of energy drives the technological development so that many fuels and energy conversion processes before judged as inadequate or even non-viable, are now competing fuels and so-called traditional processes. Thus, biomass plays an important role and is considered one of the sources of renewable energy most important of our planet. Biomass accounts for 29.2% of all renewable energy sources. The share of biomass energy from Brazil in the OIE is 13.6%, well above the world average of participation. Various types of pyrolysis processes have been studied in recent years, highlighting the process of fast pyrolysis of biomass to obtain bio-oil. The continuous fast pyrolysis, the most investigated and improved are the fluidized bed and ablative, but is being studied and developed other types in order to obtain Bio-oil a better quality, higher productivity, lower energy consumption, increased stability and process reliability and lower production cost. The stability of the product bio-oil is fundamental to designing consumer devices such as burners, engines and turbines. This study was motivated to produce Bio-oil, through the conversion of plant biomass or the use of its industrial and agricultural waste, presenting an alternative proposal for thermochemical pyrolysis process, taking advantage of particle dynamics in the rotating bed that favors the right gas-solid contact and heat transfer and mass. The pyrolyser designed to operate in a continuous process, a feeder containing two stages, a divisive system of biomass integrated with a tab of coal fines and a system of condensing steam pyrolytic. The prototype has been tested with sawdust, using a complete experimental design on two levels to investigate the sensitivity of factors: the process temperature, gas flow drag and spin speed compared to the mass yield of bio-oil. The best result was obtained in the condition of 570 oC, 25 Hz and 200 cm3/min, temperature being the parameter of greatest significance. The mass balance of the elementary stages presented in the order of 20% and 37% liquid pyrolytic carbon. We determined the properties of liquid and solid products of pyrolysis as density, viscosity, pH, PCI, and the composition characterized by chemical analysis, revealing the composition and properties of a Bio-oil.

Pirólise rápida catalítica do capim elefante utilizando materiais mesoporosos e óxidos metálicos para deoxigenação em bio-óleo

The fast pyrolysis of lignocellulosic biomass is a thermochemical conversion process for production energy which have been very atratactive due to energetic use of its products: gas (CO, CO2, H2, CH4, etc.), liquid (bio-oil) and charcoal. The bio-oil is the main product of fast pyrolysis, and its final composition and characteristics is intrinsically related to quality of biomass (ash disposal, moisture, content of cellulose, hemicellulose and lignin) and efficiency removal of oxygen compounds that cause undesirable features such as increased viscosity, instability, corrosiveness and low calorific value. The oxygenates are originated in the conventional process of biomass pyrolysis, where the use of solid catalysts allows minimization of these products by improving the bio-oil quality. The present study aims to evaluate the products of catalytic pyrolysis of elephant grass (Pennisetum purpureum Schum) using solid catalysts as tungsten oxides, supported or not in mesoporous materials like MCM-41, derived silica from rice husk ash, aimed to reduce oxygenates produced in pyrolysis. The biomasss treatment by washing with heated water (CEL) or washing with acid solution (CELix) and application of tungsten catalysts on vapors from the pyrolysis process was designed to improve the pyrolysis products quality. Conventional and catalytic pyrolysis of biomass was performed in a micro-pyrolyzer, Py-5200, coupled to GC/MS. The synthesized catalysts were characterized by X ray diffraction, infrared spectroscopy, X ray fluorescence, temperature programmed reduction and thermogravimetric analysis. Kinetic studies applying the Flynn and Wall model were performed in order to evaluate the apparent activation energy of holoceluloce thermal decomposition on samples elephant grass (CE, CEL and CELix). The results show the effectiveness of the treatment process, reducing the ash content, and were also observed decrease in the apparent activation energy of these samples. The catalytic pyrolysis process converted most of the oxygenate componds in aromatics such as benzene, toluene, ethylbenzene, etc